Synthetic waxes and method of preparing the same



Patented J une,22, l 948 s it? SYNTHETIC WAXES AND METHOD OF PREPARINGTHE SAME George J. Bohrer, Troy, N. Y.,

assignor to General Electric Company, a corporation of New York NoDrawing. Application July 4, 1945, Serial No. 603,240

. invention relates to new and useful waxlike materials or syntheticwaxes and to a method of preparing the same. More particularly the in-Vention is concerned with compositions or products comprising a wax-likematerial obtained by effecting reaction under heat, more particularlyuntil an acid number not substantially exceeding 35 has been obtained,between tetrachlorm phthalic anhydride and a mixture of monoaminesincluding essentially a plurality of monoamyl amines havin an initialboiling point of at least 84 C., at least 95 per cent distilling offbelow 100 C. and a final boiling point not higher than 110 C. Thereact-ants are employed in substantially equivalent molar proportions orwith a slight molar excess of the amine reactant.

It was known prior to my invention that synthetic waxes could beprepared by effecting reaction under heat between an aliphaticpolyamine, specifically propylene diamine, and a nuclearly halogenated,specifically nuclearly chlorinated, aromatic monocarboxylic acid orortho dicarboxylic acid, more particularly benzene-odicarboxylic acid(phthalic acid), or an acid hallde of such acids, e. g.,trichlorobenzoyl chloride. Such waxes are more fully described and arespecifically claimed in the copending application of Murray M. Sprung,Serial No. 495,045, filed July 16, 1943, now U. S. Patent 2,408,700,issued October 1, 1946, and assigned to the same assignee as the presentinvention. 7

I have discovered that synthetic axes which are non-toxic andnon-irritating to the skin of the average person can be prepared byeffecting reaction under heat, more particularly until an acid numbernot substantially exceeding 35 has been obtained, betweentetrachlorophthalic anhydride and a mixture of monoamines including aplurality of monoamyl amines having the distillation characteristicsmentioned in the first paragraph of this specification. I have alsosurprisingly discovered that the properties of the end product can beimproved, e. g., the melting point can be increased, withoutdetrimentally affecting the other useful properties, by incorporating anaromatic monoamine. specifically aniline, into the reaction mixture inaddition to the aforementioned plurality of monoamyl amines. I

The synthetic waxes :of this invention have a high melting point, themelting point being of the order of 120 C. and above. They are stable attemperatures at least as high as their melting point, and show excellentwater resistance and dielectric strength. When applied to a base, for

' 6 Claims. (Cl. 260-326) instance wood, metal (e. g., iron, steel,brass, etc.) and the like, a surface finish having a high gloss isobtained. The substantially neutral, waxy end products, the acid numbersof which may range, for example, from 0 or approximately 0 to orthcreabouts are mixtures or complexes of N-substitutedtetrachlorophthalimides, the N-substituent grouping of the individualtetrachlorophthalimide corresponding to one or another of thehydrocarbon substituents of the monoamines employed. The individualN-substituted tetrachlorophthalimide, in pure state, may be repre'-sented by the following general formula:

where R represents a phenyl radical or a hydrocarbon radical derivedfrom normal or isomeric monoamyl amine.

The mixture of monoamyl amines used in producing my new synthetic waxesis sold by'The Sharples Solvents Corporation, Philadelphia, Pa., underthe following specifications:

It is a mixture of the various monoamyl amines including:

Approximate boiling point, C.

Tertiary amyl amine 82 Secondary isoamyl amine 87 'Z-aminopentane 89B-aminopentane 8 90 Active amyl amine 94 Isoamyl amine Normal amyl amine104 In order that those skilled in the art better may understand how thepresent inventionmay be carried into effect, the following examples aregiven by way of illustration and not by way of limitation. All parts andpercentages are by .weight. The mixture of monoamyl amines alt-anthemsHelp Example 1 Parts Inert diluent, specifically Solvesso #1 1 1,750Tetrachlorophthalic anhydride 1,750 Mixture of monoamyl amines 550 1Solvesso #1 is a hydrocarbon solvent produced and sold by The StandardOil Company of New Jersey, New York, N. Y. It meets the followingspecifications Specific gravity (15.5/15.5 C.) 0.8200.83O DistillationInitial boiling point, minimum 90% distilled off, maximunn End point,maximum Aniline No., maximum 2 This amount of the mixture of monoamylamines provides 3.4% excess over that theoretically required forreaction with tetrachlorophthalic anhydride to form a mixture ofN-substituted tetrachlorophthalimides.

The above ingredients were added, in the order given, to a reactionvessel provided with stirring apparatus and a reflux condenser. Thetetrachlorophthalic anhydride was dispersed with stirring in the inertdiluent, after which the mixture of monoamyl amines was added withvigorous stirring to the closed vessel at such a rate that there was noloss of amine from the condenser. The ingredients were heated togetherunder reflux at the boiling temperature of the mass for about 2 hours.The water of reaction, diluent and any unreacted amine were now removedby distillation at atmospheric pressure. When the liquid temperature hadreached about 145 to 150 C., vacuum was gradually applied whilemaintaining the temperature of the mass at about 140 to 145 C. When nomore distillate could be obtained, the reaction product was withdrawnfrom the reaction vessel and allowed to solidify. The solid material wasa synthetic wax containing about 40 per cent combined chlorine andhaving an acid number of 32 (with phenol red as indicator) and asolidification point of 128 to 130 C.

Example 2 Parts Inert diluent, specifically So1vesso#1 150Tetrachlorophthalic anhydride 143 Mixture of monoamyl amines 41 Aniline5 The procedure was essentially the same as that described underExample 1. The mixed monoamyl amines and aniline in the above formulaare in the molar ratio of about 9 mole of the former to 1 mol of thelatter. The aniline provides an end product having a higher meltingpoint and a higher solidification point than is possible with themixture of monoamyl amines alone, as evidenced by the fact that the waxyreaction product of this example had a solidification point of 144 to148 C. It's acid number was about 25.

The molar ratio of aniline to the mixture of monoamyl amines may bevaried as desired or as conditions may require in order to obtain asynthetic wax having the particular increase in melt- "ing point wanted.Thus, the aniline and mixed monoamyl amines may be employed in molarratios varying, for example, from 1 mol of the 'former to from 0.1 to100 or more mols of the latter. No particular advantage ordinarilyaccrues from the use of aniline in less than about 3 chlorophthalicanhydride and the mixture of monoamines while these ingredients areadmixed with an inert diluent such, for instance, as petroleum naphtha,coal-tar naphtha, etc., of suitable boiling point or range. It will beunderstood, of course, by those skilled in the art that the reactionalso may be carried out in the absence of an inert diluent, in whichcase the reaction is effected under substantial superatmosphencpressure.

The synthetic waxes of this invention have a wide variety of commercialapplications. For instance, they may be used in protectively coveringmetallic surfaces to prevent corrosion and in treating wood to preventdecay. The fire-proof character of these waxes makes them especiallysuitable for use, alone or with other ingredients, e. g., a volatilesolvent, in coating or coating and impregnating fabric and other textilematerials, e. g., materials comprising natural or synthetic fibers. Theymay be used in treating filaments, threads, yarns, etc., of cotton,Wool, silk, linen, nylon, rayon, glass, Aralac, Saran, etc, or fabricsWoven or otherwise formed from such materials or combinations thereof.They may be used as modifiers of other materials, e. g., paraffin wax,asphalt or other bituminous materials of petroleum or coal-tar origin,to impart improved properties thereto. They also may be employed in themanufacture of carbon papers, for lubricating molds, as a dielectricmaterial alone or in combination with other dielectrics, e. g., oils,paper, Cellophane, cellulose esters, e. g., cellulose acetate, etc,cellulose ethers, e. g., ethyl cellulose, etc., glass fibers, asbestos,natural and synthetic resins, etc., as a component of varnishes,enamels, lacquers, paints and other liquid coating compositions, as aningredient of furniture polishes, floor polishes, automobile polishes,etc., and for numerous other purposes. They are especially suit able foruse in compositions such as are disclosed and claimed in my copcndingapplication Serial No, 603,239, filed concurrently herewith and assignedto the same assignee as the present invention.

What I claim as new and desire to secure by Letters Patent of the UnitedStates is:

1. A product comprising a wax-like material having an acid number below35 and a melting point of the order of C. and above, which is stable attemperatures at least as high as its melting point, the said materialcomprising a complex, heat-reacted mixture of N-amyl-substitutedtetrachlorophthalimides corresponding to the general formula where Rrepresents a five-membered hydrocarbon radical derived from normal andisomeric monoamyl amines, the said wax-like material having beenobtained by interaction under heat between tetrachlorophthalic anhydrideand a mixture of monoamines including a plurality of monoamyl aminesconsisting essentially of tertiary amyl amine, secondary isoamyl amine,z-aminopentane, B-aminopentane, active amyl amine, isoamyl amine, andnormal amyl amine, the said mixture of amines having an initial boilingpoint of at least 84 C., at least 95 per cent distilling oif below 1000., and a final boiling point not higher than 110 C.

2. The method of preparing new wax-like materials which compriseseffecting reaction, until an acid number not substantially exceeding 35has been obtained, between tetrachlorophthalic anhydride and a mixtureof monoamines including essentially a plurality of monoamyl amineshaving an initial boiling point of at least 84 C., at least 95 per centdistilling off below 100 C. and a final boiling point not higher than110 C.

3. A waxy material having an acid number below 35 and a melting point ofthe order of 120 C. and above, which is stable at temperatures at leastas high as its melting point, the said material comprising a complex,heat-reacted mixture of N-phenyl tetrachlorophthalimide and a mixture ofN-amyl tetrachlorophthalimides corresponding to the general formulawhere R represents a five-membered hydrocarbon radical derived fromnormal and isomeric monoamyl amines, the said wax-like material havingbeen obtained by interaction under heat between tetrachlorophthalicanhydride and a mixture of monoamines consisting essentially of anilineand a mixture of monoamyl amines including essentially tertiary amylamine, secondary isoamyl amine, Z-aminopentane, S-aminopentane, activeamyl amine, isoamyl amine, and normal amyl amine, the said mixture ofamyl amines having an initial boiling point of at least 84 C., at least95 per cent distilling off below 100 C., and a final boiling point nothigher than 110 C.

4. A method as in claim 2 wherein the reaction between thetetrachlorophthalic anhydride and the mixture of monoamines is effectedunder reflux while the said ingredients are admixed with a diluent whichis inert to the reactants during the reaction, and at the boilingtemperature of the diluted reaction mass.

5. The method which comprises dispersing tetrachlorophthalic anhydridein a liquid hydro carbon diluent, adding thereto a mixture of monoamylamines, having an initial boiling point of at least 84 C., at least percent distilling oil below C., and a final boiling point not higher thanC., with vigorous stirring under conditions such that there is nosubstantial loss of said amines during the addition, the amount of thesaid mixture of monoamyl amines being such that there is a slight excessover that theoretically required for reaction with tetrachlorophthalicanhydride to form a mixture of N-substituted tetrachlorophthalimides,heating the resulting mass under reflux at the boiling temperature ofthe mass for about 2 hours, removing the water of reaction, liquidhydrocarbon diluent and unreacted amine by distillation at atmosphericpressure, removing any remaining distillate under vacuum when the liquidtemperature reaches about 145 to 150 C., said application of vacuumbeing continued while maintaining the temperature of the reaction massat about to C., withdrawing the reaction product from the reactionvessel and allowing it to solidify, the solid reaction product beingsynthetic wax containing, by weight, about 40 per cent combined chlorineand having a solidification point of 128 to 130 C.

6. A waxy material as in claim 3 wherein the aniline and the pluralityof monoamyl amines are employed in amounts corresponding to from 0.1 to100 mols of the latter for each mol of aniline.

GEORGE J. BOHRER.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Name Date Pool et al Dec. 17, 1940 OTHER-REFERENCES Chemical Abstracts, vol. 12, pp. 4'79, 480 (1918). (Copy inDiv. 6.) Citing: Pratt et al., Journal Number

